CN112552684A - Low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation and preparation and application thereof - Google Patents
Low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation and preparation and application thereof Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation and preparation and application thereof. The composite material comprises the following raw materials in percentage by weight: 44.8 to 56.2 percent of polyphenylene sulfide resin, 3 to 8 percent of toughening agent, 25 to 35 percent of low dielectric glass fiber, 0.2 to 0.6 percent of nucleating agent, 0.3 to 0.6 percent of coupling agent, 0.3 to 1 percent of lubricant and 5 to 15 percent of low melting point glass powder. The preparation method comprises the following steps: (a) premixing: mixing polyphenylene sulfide resin and a toughening agent according to a ratio, and then adding a coupling agent for mixing to obtain a premix; (b) mixing material treatment: adding other raw materials except the low dielectric glass fiber into the premix according to the proportion for blending to obtain a uniform mixture; (c) and (3) extruding and granulating: extruding and granulating the uniform mixture obtained in the step (b) through a double-screw extruder, and meanwhile, feeding low-dielectric glass fiber in a side feeding mode to obtain the composite material.
Description
Technical Field
The invention relates to the technical field of polyphenylene sulfide materials, in particular to a low-linear-expansion-coefficient polyphenylene sulfide composite material special for micro-arc oxidation and preparation and application thereof.
Background
The micro-arc oxidation technology is a surface treatment technology developed by anodic oxidation, is mainly applied to the surface of light metal, adopts high voltage to carry out discharge treatment, utilizes the instantaneous high-temperature sintering action of a micro-arc area on the surface of the metal to form a compact ceramic membrane on the surface of the metal, has better bonding force with a paint spraying layer, better pollution resistance and corrosion resistance, and has better application prospect on notebook computer back plates and automobile parts.
At present, most notebook back boards are made of aluminum alloy or magnesium alloy materials, the products are attractive, the surfaces of the notebook back boards are painted into various colors, however, the surface paint layers are easy to fall off in the using process, the attractiveness of the products is affected, therefore, the micro-arc oxidation process of the aluminum alloy or the magnesium alloy is necessary, the firmness of the paint layer is increased, the requirements of the notebook computer backboard antenna on wireless network transmission signals are higher and higher along with the development of the 5G network, the aluminum alloy or the magnesium alloy material generates shielding property on the transmission of the antenna signals to influence the transmission of the signals, therefore, the position of the backboard antenna needs a polyphenylene sulfide (PPS) material with low dielectric property, which can resist the micro-arc oxidation process and avoid the burning of the PPS surface caused by the micro-arc oxidation, meanwhile, the PPS material and the main body light metal are required to have similar linear thermal expansion coefficients, so that the notebook backboard can be prevented from cracking.
The PPS material as a high-performance engineering plastic plays an important role in the lightweight development of replacing steel with plastic, at present, a plurality of relevant patent documents are researched at home and abroad in relation to the preparation of the polyphenylene sulfide composite material special for micro-arc oxidation, and the problem of ablation resistance of the material is mainly focused or only the problem of linear expansion coefficient of the material is focused.
For example, chinese patent application publication No. CN111019347A discloses an ablation-resistant polyphenylene sulfide composite material and a preparation method thereof, wherein the raw materials include: 20 to 70 percent of polyphenylene sulfide, 15 to 50 percent of alkali-free glass fiber and 5 to 40 percent of poly m-xylylene adipamide. According to the invention, the ablation resistance of the surface of the PPS material is improved through the synergistic effect of poly (m-xylylene adipamide), the polyphenylene sulfide composite material obtained by the preparation method can bear the high-temperature and high-pressure action generated in the micro-arc oxidation process, has good ablation resistance, has the line ablation rate of below 0.062mm/s, and is simple in preparation process. The patent mainly researches the ablation resistance problem of the material surface, does not research the dielectric property and the linear expansion coefficient of a product, and limits the application of the material in some fields.
Also, as disclosed in chinese patent application publication No. CN111073288A, a low linear expansion coefficient polyphenylene sulfide composite material and a preparation method thereof include the following components and raw materials in parts by weight: 100 parts of matrix resin; 0.1-1 part of antioxidant; 0.5-2 parts of a lubricant; 30-70 parts of phlogopite. Compared with the prior art, the low-linear-expansion-coefficient polyphenylene sulfide composite material and the preparation method thereof disclosed by the invention have the advantages that the linear expansion coefficient of the PPS material is reduced by adopting the high-filling inorganic minerals, so that the product of the PPS composite material is higher in size stability. The patent only aims at the modification research of reducing the linear expansion coefficient of the PPS material, does not research the toughness, the strength and the ablation resistance of the material, and limits the application of the PPS material in some fields.
Disclosure of Invention
Aiming at the technical problems, the invention provides the low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation, which can resist a micro-arc oxidation process, can avoid scorching on the surface of the PPS composite material caused by micro-arc oxidation, has similar linear thermal expansion coefficient with main body light metals such as aluminum, magnesium and the like, and can avoid cracking of a notebook backboard when being used for a notebook computer backboard antenna.
The low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation comprises the following raw materials in percentage by weight:
the chlorine content of the polyphenylene sulfide resin is less than 1000 ppm;
the low dielectric glass fiber has a dielectric constant of less than 4.5 and a linear expansion coefficient of less than 3.5 × 10-6The length is 3-6 mm;
the nucleating agent is at least one of barium sulfate with D50 being 0.9-1.2 mu m, fumed silica and talc powder with more than 3000 meshes, and the nucleating agent is modified by a silane coupling agent;
the linear expansion coefficient of the low-melting-point glass powder is 8.5 multiplied by 10-6～14×10-6The glass transition temperature is less than or equal to 450 ℃, and the low-melting-point glass powder is firstly softened and covered on the surface of the PPS before the decomposition temperature of 10 wt% of the polyphenylene sulfide TG is 550 ℃.
The low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation has excellent mechanical property, ablation resistance, low dielectric constant, low dielectric loss and low linear expansion coefficient, is easy to perform injection molding, has good mechanical property and small warpage deformation, and meets the use requirements of customers.
In order to adapt the reinforced polyphenylene sulfide composite material to the use characteristics of micro-arc oxidation treatment, the chlorine content of the polyphenylene sulfide resin used is limited to be less than 1000 ppm. In the reinforced polyphenylene sulfide composite material system, the specific low dielectric glass fiber provides mechanical properties such as better mechanical strength for the material on one hand, and enables the composite material to have relatively low dielectric constant and dielectric loss on the other hand, and simultaneously, compared with the conventional alkali-free glass fiber, the linear expansion coefficient can be further reduced; the specific nucleating agent can promote the crystallization of the PPS material, reduce the linear expansion coefficient of the material and provide dimensional stability for the material, and compared with an organic nucleating agent, the inorganic nucleating agent is low in price; when the composite material is heated, the specific low-melting-point glass powder can be melted before the PPS material is carbonized, and the melted low-melting-point glass powder covers the surface of the PPS material, so that the probability and degree of surface carbonization and ablation of the PPS material are reduced.
Preferably, the melt flow rate of the polyphenylene sulfide resin is 70-300 g/10min at 300 ℃ under the condition of 2.16kg, the flowability is moderate, and the use characteristic is suitable for micro-arc oxidation treatment.
Preferably, the toughening agent is an ethylene-glycidyl methacrylate copolymer (E-GMA) and/or an ethylene-glycidyl methacrylate-methyl acrylate terpolymer (E-GMA-MA). The ethylene-glycidyl methacrylate copolymer is preferably Sumitomo BF-E, and the ethylene-glycidyl methacrylate-methyl acrylate terpolymer (E-GMA-MA) is preferably Sumitomo BF-7L.
Preferably, the coupling agent is one or more of aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560) and gamma-methacryloxypropyltrimethoxysilane (KH 570).
Preferably, the lubricant is one or two of polyol ester lubricant, silicone lubricant and oxidized polyethylene wax, such as pentaerythritol stearate (PETS), high molecular weight silicone powder (such as GM-100), and oxidized polyethylene wax (such as Uniclear 816).
According to the research of the invention, the sum of the qualities of the low-dielectric glass fiber and the low-melting-point glass powder simultaneously influences the mechanical property, the ablation resistance, the linear expansion coefficient, the dielectric constant and the dielectric loss of the reinforced polyphenylene sulfide composite material. Further preferably, in the low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation, the sum of the mass of the low dielectric glass fiber and the mass of the low melting point glass powder is 40-45% of the total mass of the raw materials.
Under the conditions of the optimized raw material types and the optimized proportion, the obtained polyphenylene sulfide composite material with the low linear expansion coefficient special for micro-arc oxidation has the mechanical property, ablation resistance, low linear expansion coefficient, low dielectric constant (lower than 4.0) and low dielectric loss (lower than 0.006) which are most suitable for micro-arc oxidation treatment.
The invention also provides a preferable preparation method of the low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation, which comprises the following steps:
(a) premixing: mixing polyphenylene sulfide resin and a toughening agent according to a ratio, and then adding a coupling agent for mixing to obtain a premix;
(b) mixing material treatment: adding other raw materials except the low dielectric glass fiber into the premix according to the proportion for blending to obtain a uniform mixture;
(c) and (3) extruding and granulating: and (c) extruding and granulating the uniform mixture obtained in the step (b) through a double-screw extruder, and meanwhile, feeding low-dielectric glass fiber in a side feeding manner to obtain the low-linear-expansion-coefficient polyphenylene sulfide composite material special for micro-arc oxidation.
In order to fully and uniformly mix the coupling agent and the resin matrix and avoid the problem that the coupling agent is not easy to be uniformly mixed with the subsequently added powder to cause the performance of the product to be reduced, the invention carries out the premixing in the step (a).
Research shows that in addition to the factors such as the formula, the feeding sequence and the process, the bending modulus, the impact property and other properties of the polyphenylene sulfide composite material can be further improved by adjusting and controlling the technical parameters such as the length-diameter ratio of a screw, the combination of the screws, the temperature of each section and the like of a double-screw extruder, the feeding position of the low dielectric glass fiber and the like.
Preferably, the twin-screw extruder comprises nine barrels, wherein the low dielectric glass fiber is fed into the 5 th barrel in a side feeding mode;
the length-diameter ratio of the screws of the double-screw extruder is 40:1, and the configuration requirements of the shear block of the screw combination are as follows: the 1 st to 4 th sections of the screw cylinders comprise 2 groups of shear blocks, and each group comprises 3 shear blocks; the 6 th to 9 th sections of the screw cylinder also comprise 2 groups of shear blocks, wherein one group comprises 2 shear blocks, and the other group comprises 3 shear blocks;
temperature setting of the twin-screw extruder: the temperatures of the first zone to the ninth zone are 270 + -5 ℃, 290 + -5 ℃, 280 + -5 ℃, the die temperature is 290-305 ℃, and the rotation speed of the host screw is 250-350 r/min.
The low-linear-expansion-coefficient polyphenylene sulfide composite material special for micro-arc oxidation, prepared by the preparation method, is easy to perform injection molding, good in mechanical property, low in linear expansion coefficient, ablation-resistant, small in warping deformation, low in dielectric constant and low in dielectric loss, and meets the use requirements of customers.
The invention also provides application of the low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation in a micro-arc oxidation resistant notebook computer backboard antenna.
The notebook backboard is preferably made of aluminum alloy or magnesium alloy materials, the dielectric constant of the low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation is lower than 4.0, and the dielectric loss is lower than 0.006. The low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation has better adaptability with the alloy material.
Compared with the prior art, the invention has the main advantages that:
1. compared with the existing micro-arc oxidation PPS, the low-dielectric glass fiber provided by the invention is added into PPS as a reinforcing component, so that the product has lower dielectric constant and dielectric loss and lower linear expansion coefficient. At present, most of glass fibers used in the prior art are alkali-free glass fibers, the dielectric constant is 6-7, and the linear expansion coefficient is 5.5 multiplied by 10-6The low-dielectric glass fiber has a dielectric constant of less than 4.5 and a linear expansion coefficient of less than 3.5 x 10-6。
2. The invention adopts the low-melting-point glass powder, so that the product avoids the dimensional instability caused by water absorption and has lower linear expansion coefficient of 8.5 multiplied by 10-6～14×10-6Therefore, the PPS composite material has a linear expansion coefficient which is relatively close to that of light metals such as aluminum, magnesium and the like. During the process of micro-arc oxidation, the high temperature generated by micro-arc oxidation can melt the low-melting-point glass powder to cover the PPS surface, so that the reduction of the content of the low-melting-point glass powder can be realizedThe formation of surface carbonization of the PPS product avoids or reduces scorching.
3. The preparation method can be realized by adopting the existing equipment double-screw extruder, the full dispersion of the polyphenylene sulfide composite material is realized through the formula, screw combination and production process design, the preparation is simple, the industrial large-scale production is easy, and the preparation method has wide application prospect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
In the following examples and comparative examples, the following brands of raw materials were specifically selected:
polyphenylene sulfide PPS is prepared from resin 1350C, MI: 150g/10min (300 ℃, 2.16kg), the chlorine content is less than 1000 ppm;
the toughening agent is BF-E of Sumitomo;
the low-dielectric glass fiber is made of Chongqing international composite material ECS 309-3-K/HL;
the nucleating agent is barium sulfate with the particle size (D50) of 0.9-1.2 mu m, which is obtained by modifying Qingdao red butterfly with a silane coupling agent;
the lubricant is selected from medium-blue-morning light GM-100;
the coupling agent is Nanjing total-Hich KH 560;
the low-melting-point glass powder is prepared from an Ammi micro-nano D235.
The twin-screw extruder is an NE40D/40-900 twin-screw extruder of Sichuan China science and technology Co., Ltd, and comprises nine screw barrels, the length-diameter ratio of the screws is 40:1, and the configuration requirements of the shear block of the screw combination are as follows: the 1 st to 4 th sections of the screw cylinders comprise 2 groups of shear blocks, and each group comprises 3 shear blocks; the section 6-9 barrels also contain 2 sets of cutouts, one set containing 2 cutouts and the other set containing 3 cutouts.
Comparative examples 1 to 6 and examples 1 to 6:
the polyphenylene sulfide resin and the toughening agent are mixed according to the proportion, then the coupling agent is added for premixing, then all the raw materials except the low dielectric glass fiber are added, the raw materials are put into a mixer of 100r/min for mixing for 10min, and then the mixture in the mixer is added from a feeding port of a first barrel of a double-screw extruder. The low dielectric glass fiber is added from a feeding port at the side of the fifth barrel. Temperature of each section of the cylinder of the double-screw extruder: the temperatures of the first zone to the ninth zone are 270 +/-5 ℃, 290 +/-5 ℃, 280 +/-5 ℃, the die temperature is 290-305 ℃ and the rotation speed of a main machine screw is 300 r/min. Extruding the polyphenylene sulfide by a double-screw extruder, cooling by water, granulating, placing the granules in a forced air drying oven at 100 ℃ for 4 hours to obtain the special material for the polyphenylene sulfide composite material, and preparing a test sample strip by an injection molding machine.
The weight percentage (%) of each raw material in comparative examples 1 to 6 and examples 1 to 6 is shown in tables 1 and 2 below. Comparative example 1 has no toughening agent added, comparative example 2 has excessive low dielectric glass fiber and insufficient low melting point glass powder, comparative example 3 has excessive toughening agent added, comparative example 4 has insufficient low dielectric glass fiber, comparative example 5 has no lubricant added, and comparative example 6 has excessive low melting point glass powder added.
TABLE 1
TABLE 2
The items tested, the equipment used and the reference standards are listed in table 3 below.
TABLE 3
The materials prepared in comparative examples 1 to 6 and examples 1 to 6 were tested according to the test methods described above, and the test results are shown in tables 4 and 5 below.
TABLE 4
TABLE 5
As can be seen from tables 4 and 5, the composite material has a low linear expansion coefficient, which is about 30, and is relatively close to light magnesium metal. The composite material is also improved in ablation resistance.
The materials prepared in the embodiments 1 to 6 have low linear expansion coefficient, excellent ablation resistance, dielectric constant lower than 4.0, dielectric loss lower than 0.006, high mechanical strength and good practicability, and can be applied to electronic products of micro-arc oxidation process. In comparative example 1, no compatibilizer was added, the impact strength of the material was low, and the injection molding production requirements of the micro-arc oxidized electronic product could not be met. Compared with the comparative example 1, the addition of the compatibilizer in the comparative example 2 increases the impact strength of the material, so that the toughness of the material meets the use requirement, and compared with the example 1, the low-melting-point glass powder is reduced, the content of the low-dielectric glass fiber is increased, the ceramic rate of the material is reduced after the material is subjected to high temperature, so that the ablation rate is increased, and the ablation resistance is reduced. In comparative example 3, the addition of the toughening agent increased, the impact strength of the material continued to increase, the modulus decreased, and the rigidity of the material was insufficient, while the addition of the toughening agent also increased the dielectric constant, dielectric loss, and linear expansion coefficient of the material. In comparative example 4, the decrease in the content of low dielectric glass fiber decreased the flexural modulus of the material, insufficient strength, increased the linear expansion coefficient of the material, and decreased ablation resistance, which is not suitable for micro-arc oxidation treated electronic products. In comparative example 5, no lubricating aid was added, which is mainly reflected in the problem that poor mold release is likely to occur in the injection molding of the material. In comparative example 6, too much low-melting-point glass powder is added, so that the impact strength of the product is reduced, the toughness of the material is insufficient, the processing difficulty of the material is increased, and the powder is light and difficult to process. In the embodiment, the low dielectric glass fiber with the proper proportion enables the linear expansion coefficient, the strength and the rigidity of the material to meet the use requirements of customers, the dielectric constant and the dielectric loss of the material to meet the requirements of customers, and the addition of the compatibilizer, the low-melting glass powder and the lubricant with the proper proportion can meet the requirements of the customers on the performance of the material processing, so that the material is suitable for micro-arc oxidation products, and the application field of the material is further increased.
The composite material has the characteristics of low linear expansion coefficient, excellent ablation resistance, low dielectric constant, low dielectric loss, easy injection molding, good mechanical property and small warping deformation.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. The low-linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation is characterized by comprising the following raw materials in percentage by weight:
the chlorine content of the polyphenylene sulfide resin is less than 1000 ppm;
the low dielectric glass fiber has a dielectric constant of less than 4.5 and a linear expansion coefficient of less than 3.5 × 10-6The length is 3-6 mm;
the nucleating agent is at least one of barium sulfate with D50 being 0.9-1.2 mu m, fumed silica and talc powder with more than 3000 meshes, and the nucleating agent is modified by a silane coupling agent;
the linear expansion coefficient of the low-melting-point glass powder is 8.5 multiplied by 10-6～14×10-6The glass transition temperature is less than or equal to 450 ℃.
2. The low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation according to claim 1, wherein the melt flow rate of the polyphenylene sulfide resin at 300 ℃ and 2.16kg is 70-300 g/10 min.
3. The low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation according to claim 1, wherein the toughening agent is an ethylene-glycidyl methacrylate copolymer and/or an ethylene-glycidyl methacrylate-methyl acrylate terpolymer.
4. The low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation according to claim 1 or 3, wherein the coupling agent is one or more of aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane.
5. The low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation according to claim 1, wherein the lubricant is one or two of polyol ester lubricant, silicone lubricant and oxidized polyethylene wax.
6. The polyphenylene sulfide composite material with the low linear expansion coefficient special for micro-arc oxidation as claimed in claim 1, wherein the sum of the mass of the low dielectric glass fiber and the low melting point glass powder is 40-45% of the total mass of the raw materials.
7. The preparation method of the low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation according to any one of claims 1 to 6, characterized by comprising the steps of:
(a) premixing: mixing polyphenylene sulfide resin and a toughening agent according to a ratio, and then adding a coupling agent for mixing to obtain a premix;
(b) mixing material treatment: adding other raw materials except the low dielectric glass fiber into the premix according to the proportion for blending to obtain a uniform mixture;
(c) and (3) extruding and granulating: and (c) extruding and granulating the uniform mixture obtained in the step (b) through a double-screw extruder, and meanwhile, feeding low-dielectric glass fiber in a side feeding manner to obtain the low-linear-expansion-coefficient polyphenylene sulfide composite material special for micro-arc oxidation.
8. The method of claim 7, wherein the twin screw extruder comprises nine barrels, wherein the low dielectric glass fiber is side-fed at the 5 th barrel;
the length-diameter ratio of the screws of the double-screw extruder is 40:1, and the configuration requirements of the shear block of the screw combination are as follows: the 1 st to 4 th sections of the screw cylinders comprise 2 groups of shear blocks, and each group comprises 3 shear blocks; the 6 th to 9 th sections of the screw cylinder also comprise 2 groups of shear blocks, wherein one group comprises 2 shear blocks, and the other group comprises 3 shear blocks;
temperature setting of the twin-screw extruder: the temperatures of the first zone to the ninth zone are 270 + -5 ℃, 290 + -5 ℃, 280 + -5 ℃, the die temperature is 290-305 ℃, and the rotation speed of the host screw is 250-350 r/min.
9. The application of the low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation according to any one of claims 1-6 in a micro-arc oxidation resistant notebook computer backboard antenna.
10. The application of claim 9, wherein the notebook backboard is made of an aluminum alloy or magnesium alloy material, the low linear expansion coefficient polyphenylene sulfide composite material special for micro-arc oxidation has a dielectric constant of less than 4.0 and a dielectric loss of less than 0.006.
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| CN116120747A (en) * | 2022-12-12 | 2023-05-16 | 中广核俊尔(浙江)新材料有限公司 | Heat conduction ultralow linear expansion coefficient PPS composite material for plastic cavity filter and preparation method thereof |
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| CN114231031A (en) * | 2021-11-30 | 2022-03-25 | 金发科技股份有限公司 | Foamed polyphenylene sulfide composition and preparation method and application thereof |
| CN114231031B (en) * | 2021-11-30 | 2023-09-19 | 金发科技股份有限公司 | Foaming polyphenylene sulfide composition and preparation method and application thereof |
| CN116120747A (en) * | 2022-12-12 | 2023-05-16 | 中广核俊尔(浙江)新材料有限公司 | Heat conduction ultralow linear expansion coefficient PPS composite material for plastic cavity filter and preparation method thereof |
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